Mechanism of polymerization reaction of 4-[(n-butylsulfinyl)methyl]-4′-(chloromethyl)benzene

Sang Yong Pyun, Whan G. Kim, Jin Hyun Jeong, Bong-Rae Cho

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

The polymerization reaction of 4-[(n-butylsulfinyl)methyl]-4′-(chloromethyl)benzene (1a) with t-BuONa in CH2Cl2/monomethylformamide (MMF) (4/6) was studied kinetically. The reaction proceeds in two steps; the formation of a p-quinodimethane intermediate (M) followed by the polymerization of M. Results of kinetic studies and H-D exchange experiments reveal that the 1,6-elimination proceeds by the (E1cb)irr mechanism. The rate of the disappearance of M was increased by the carbanion and S2O82-, inhibited by TEMPO and unaltered by the addition of HCl. From these results, a free radical polymerization mechanism is proposed.

Original languageEnglish
Pages (from-to)2453-2458
Number of pages6
JournalBulletin of the Korean Chemical Society
Volume29
Issue number12
Publication statusPublished - 2008 Dec 1

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methylformamide
Polymerization
Free radical polymerization
Kinetics
Experiments
benzyl chloride
TEMPO

Keywords

  • Elimination
  • Intermediate
  • Polymerization

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Mechanism of polymerization reaction of 4-[(n-butylsulfinyl)methyl]-4′-(chloromethyl)benzene. / Pyun, Sang Yong; Kim, Whan G.; Jeong, Jin Hyun; Cho, Bong-Rae.

In: Bulletin of the Korean Chemical Society, Vol. 29, No. 12, 01.12.2008, p. 2453-2458.

Research output: Contribution to journalArticle

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AB - The polymerization reaction of 4-[(n-butylsulfinyl)methyl]-4′-(chloromethyl)benzene (1a) with t-BuONa in CH2Cl2/monomethylformamide (MMF) (4/6) was studied kinetically. The reaction proceeds in two steps; the formation of a p-quinodimethane intermediate (M) followed by the polymerization of M. Results of kinetic studies and H-D exchange experiments reveal that the 1,6-elimination proceeds by the (E1cb)irr mechanism. The rate of the disappearance of M was increased by the carbanion and S2O82-, inhibited by TEMPO and unaltered by the addition of HCl. From these results, a free radical polymerization mechanism is proposed.

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